[1] Our understanding of the activation of aerosol particles into cloud drops during the formation of warm cumulus clouds presently has a limited observational foundation. Detailed observations of aerosol size and composition, cloud microphysics and dynamics, and atmospheric thermodynamic state were collected in a systematic study of 21 cumulus clouds by the Center for Interdisciplinary Remotely-Piloted Aircraft Studies (CIRPAS) Twin Otter aircraft during NASA's Cirrus Regional Study of Tropical Anvils and Cirrus Layers - Florida Area Cirrus Experiment (CRYSTAL-FACE). An "aerosol-cloud'' closure study was carried out in which a detailed cloud activation parcel model, which predicts cloud drop concentration using observed aerosol concentration, size distribution, cloud updraft velocity, and thermodynamic state, is evaluated against observations. On average, measured droplet concentration in adiabatic cloud regions is within 15% of the predictions. This agreement is corroborated by independent measurements of aerosol activation carried out by two cloud condensation nucleus (CCN) counters on the aircraft. Variations in aerosol concentration, which ranged from 300 to 3300 cm(-3), drives large microphysical differences ( 250 2300 cm(-3)) observed among continental and maritime clouds in the South Florida region. This is the first known study in which a cloud parcel model is evaluated in a closure study using a constraining set of data collected from a single platform. Likewise, this is the first known study in which relationships among aerosol size distribution, CCN spectrum, and cloud droplet concentration are all found to be consistent with theory within experimental uncertainties much less than 50%. Vertical profiles of cloud microphysical properties ( effective radius, droplet concentration, dispersion) clearly demonstrate the boundary layer aerosol's effect on cloud microphysics throughout the lowest 1 km of cloud depth. Onboard measurements of aerosol hygroscopic growth and the organic to sulfate mass ratio are related to CCN properties. These chemical data are used to quantify the range of uncertainty associated with the simplified treatment of aerosol composition assumed in the closure study.

[1] We used a one-dimensional (1-D) cloud parcel model to assess the impact of biomass-burning aerosol on cloud properties in the Amazon Basin and to identify the physical and chemical properties of the aerosol that influence droplet growth. Cloud condensation nuclei (CCN) measurements were performed between 0.15% and 1.5% supersaturation at ground-based sites in the states of Amazonas and Rondonia, Brazil during several field campaigns in 1998 and 1999 as part of the Large-Scale Biosphere - Atmosphere (LBA) Experiment in Amazonia. CCN concentrations measured during the wet season were low and resembled concentrations more typical of marine conditions than most continental sites. During the dry season, smoke aerosol from biomass burning dramatically increased CCN concentrations. The modification of cloud properties, such as cloud droplet effective radius and maximum supersaturation, is most sensitive at low CCN concentrations. Hence, we could expect larger interannual variation of cloud properties during the wet season that the dry season. We found that differences between CCN spectra from forested and deforested regions during the wet season are modest and result in modifications of cloud properties that are small compared to those between wet and dry seasons. Our study suggests that the differences in surface albedo, rather than cloud albedo, between forested and deforested regions may dominate the impact of deforestation on the hydrological cycle and convective activity during the wet season. During the dry season, on the other hand, cloud droplet concentrations may increase by up to 7 times, which leads to a model-predicted decrease in cloud effective radius by a factor of 2. This could imply a maximum indirect radiative forcing due to aerosol as high as ca. -27 W m(-2) for a nonabsorbing cloud. Light-absorbing substances in smoke darken the Amazonian clouds and reduce the net radiative forcing, and a comparison of the Advanced Very High Resolution Radiometer (AVHRR) analysis and our modeling studies suggests that absorption of sunlight due to smoke aerosol may compensate for about half of the maximum aerosol effect. Sensitivity tests show that complete characterization of the aerosol is necessary when kinetic growth limitations become important. Subtle differences in the chemical and physical makeup are shown to be particularly influential in the activation and growth behavior of the aerosol. Knowledge of the CCN spectrum alone is not sufficient to fully capture the climatic influence of biomass burning.

The composition and properties of sea spray aerosol, a major component of the atmosphere, are often controlled by marine biological activity; however, the scope of impacts that ocean chemistry has on the ability for sea spray aerosol to act as cloud condensation nuclei (CCN) is not well understood. In this study, we utilize a mesocosm experiment to investigate the impact of marine biogeochemical processes on the composition and mixing state of sea spray aerosol particles with diameters<0.2 mu m produced by controlled breaking waves in a unique ocean-atmosphere facility. An increase in relative abundance of a distinct, insoluble organic particle type was observed after concentrations of heterotrophic bacteria increased in the seawater, leading to an 86 +/- 5% reduction in the hygroscopicity parameter () at 0.2% supersaturation. Aerosol size distributions showed very little change and the submicron organic mass fraction increased by less than 15% throughout the experiment; as such, neither of these typical metrics can explain the observed reduction in hygroscopicity. Predictions of the hygroscopicity parameter that make the common assumption that all particles have the same bulk organic volume fractions lead to overpredictions of CCN concentrations by 25% in these experiments. Importantly, key changes in sea spray aerosol mixing state that ultimately influenced CCN activity were driven by bacteria-mediated alterations to the organic composition of seawater.

[ 1] Measurements of aerosol and cloud properties in the Eastern Pacific Ocean were taken during an airborne experiment on the University of Wyoming's King Air during April 2004 as part of the Cloud Indirect Forcing Experiment (CIFEX). We observed a wide variety of aerosols, including those of long-range transport from Asia, clean marine boundary layer, and North American emissions. These aerosols, classified by their size distribution and history, were found in stratified layers between 500 to 7500 m above sea level and thicknesses from 100 to 3000 m. A comparison of the aerosol size distributions to measurements of cloud condensation nuclei (CCN) provides insight to the CCN activity of the different aerosol types. The overall ratio of measured to predicted CCN concentration (NCCN) is 0.56 +/- 0.41 with a relationship of N-CCN,N- measured = N-CCN, predicted(0.846 +/- 0.002) for 23 research flights and 1884 comparisons. Such a relationship does not accurately describe a CCN closure; however, it is consistent with our measurements that high CCN concentrations are more influenced by anthropogenic sources, which are less CCN active. While other CCN closures have obtained results closer to the expected 1: 1 relationship, the different aerosol types ( and presumably differences in aerosol chemistry) are responsible for the discrepancy. The measured N-CCN at 0.3% supersaturation (S-c) ranged from 20 cm(-3) (pristine) to 350 cm(-3) ( anthropogenic) with an average of 106 +/- 54 cm(-3) over the experiment. The inferred supersaturation in the clouds sampled during this experiment is similar to 0.3%. CCN concentrations of cloud-processed aerosol were well predicted using an ammonium sulfate approximation for S-c <= 0.4%. Predicted N-CCN for other aerosol types (i.e., Asian and North American aerosols) were high compared to measured values indicating a less CCN active aerosol. This study highlights the importance of chemical effects on CCN measurements and introduces a CCN activation index as a method of classifying the efficiency of an aerosol to serve as CCN relative to an ammonium sulfate particle. This index ranged from close to unity for cloud processed aerosols to as low as 0.31 for aged aerosols transported from Asia. We also compare the performance of two CCN instruments ( static thermal diffusion chamber and streamwise continuous flow chamber) on a 45 minute level leg where we observe an aged layer and a nucleation event. More than 50% of the aged aerosol served as CCN at 0.2% S-c, primarily owing to their large size, while CCN concentrations during the nucleation event were close to 0 cm(-3). CCN concentrations from both instruments agreed within instrument errors; however, the continuous flow chamber effectively captured the rapid transition in aerosol properties.

Organic material, about half of which is water soluble, constitutes nearly 80% of the wet-season aerosol mass in the Amazon Basin, while soluble inorganic salts (predominantly ammonium bisulfate) represent about 15%. A detailed analysis of number distributions and the size-dependent chemical composition of the aerosol indicates that, in principle, the sulfate fraction could account for most of the cloud condensation nuclei (CCN) activity. Uncertainty about the chemical speciation of the water-soluble organic component precludes a rigorous analysis of its contribution to nucleation activity. Within reasonable assumptions, we can, however, predict a similar contribution of the organic component to CCN activity as that from sulfate. Because of the nonlinear dependence of droplet nucleation behavior on solute amount, the nucleation activity cannot be attributed uniquely to the inorganic or organic fractions. The role of water-soluble organic compounds as surfactants, however, may be significant (especially in the case of biomass-burning aerosol) and more field measurements are needed to quantify their effects on the surface tension of ambient aerosols. The parametric dependence of the CCN spectra on the physical and chemical properties of the aerosol show that the number distribution, soluble content of the aerosol, and surface tension effects all play an important role in determining CCN spectra.

Submicron aerosol size distributions, CN and CCN concentrations at a constant supersaturation of 0.6% were measured at a relatively remote coastal site at Gosan in Jeju Island, Korea, during the ABC-EAREX from 11 March to 8 April 2005. The average CN concentrations were 6088 +/- 3988, 5231 +/- 2454 and 3513 +/- 1790 cm(-3), respectively, for the three major air mass types classified by their origins. The corresponding CCN concentrations were 2393 +/- 1156, 2897 +/- 1226 and 1843 +/- 585 cm(-3). The type III air mass was the closest to maritime origins, but these lowest concentrations at Gosan were an order of magnitude higher than those of clean marine boundary layer, indicating that regardless of air mass designation springtime submicron aerosols at Gosan were under steady continental influences. Distinct new particle formation and growth events occurred on 6 d, when clear sky weather conditions prevailed that brought air from northern China, Mongolia or Russia by anticyclonic circulations. Simultaneous occurrence of these events at a western coastal site in the Korean Peninsula 350 km north of Gosan suggests that these events were not local but at least regional-scale events. CCN concentrations were predicted with the aerosol size distributions and the assumption of particles being composed of ( NH(4))(2)SO(4). The predicted to measured CCN concentration ratio was 1.27 +/- 0.29 and the r(2) was 0.77 for the whole measurement period. The type I air mass that has the most continental influences showed a slight tendency to overpredict CCN concentrations but the good agreement overall suggests that springtime Gosan aerosols act almost like ammonium sulfate as far as CCN activity is concerned, almost regardless of air mass origin.

The spontaneous growth of cloud condensation nuclei (CCN) into cloud droplets under supersaturated water vapour conditions is described by classic Kohler theory(1,2). This spontaneous activation of CCN depends on the interplay between the Raoult effect, whereby activation potential increases with decreasing water activity or increasing solute concentration, and the Kelvin effect, whereby activation potential decreases with decreasing droplet size or increases with decreasing surface tension, which is sensitive to surfactants(1). Surface tension lowering caused by organic surfactants, which diminishes the Kelvin effect, is expected to be negated by a concomitant reduction in the Raoult effect, driven by the displacement of surfactant molecules from the droplet bulk to the droplet-vapour interface(3,4). Here we present observational and theoretical evidence illustrating that, in ambient air, surface tension lowering can prevail over the reduction in the Raoult effect, leading to substantial increases in cloud droplet concentrations. We suggest that consideration of liquid-liquid phase separation, leading to complete or partial engulfing of a hygroscopic particle core by a hydrophobic organic-rich phase, can explain the lack of concomitant reduction of the Raoult effect, while maintaining substantial lowering of surface tension, even for partial surface coverage. Apart from the importance of particle size and composition in droplet activation, we show by observation and modelling that incorporation of phase-separation effects into activation thermodynamics can lead to a CCN number concentration that is up to ten times what is predicted by climate models, changing the properties of clouds. An adequate representation of the CCN activation process is essential to the prediction of clouds in climate models, and given the effect of clouds on the Earth's energy balance, improved prediction of aerosol-cloud-climate interactions is likely to result in improved assessments of future climate change.